CN1142866C - Valuable printed document with luminous discriminator - Google Patents

Valuable printed document with luminous discriminator Download PDF

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Publication number
CN1142866C
CN1142866C CNB998001015A CN99800101A CN1142866C CN 1142866 C CN1142866 C CN 1142866C CN B998001015 A CNB998001015 A CN B998001015A CN 99800101 A CN99800101 A CN 99800101A CN 1142866 C CN1142866 C CN 1142866C
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CN
China
Prior art keywords
printing
luminescent substance
valuable document
false proof
proof device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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CNB998001015A
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Chinese (zh)
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CN1255897A (en
Inventor
���ٿˡ�����
威蒂克·考尔
Ŀ�
格哈德·施文克
格哈德·斯滕泽尔
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Jiejia German Currency Technology Co Ltd
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Giesecke and Devrient GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S283/00—Printed matter
    • Y10S283/901—Concealed data
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/916—Fraud or tamper detecting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/22—Nonparticulate element embedded or inlaid in substrate and visible
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24835—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including developable image or soluble portion in coating or impregnation [e.g., safety paper, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24934—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Accounting & Taxation (AREA)
  • Business, Economics & Management (AREA)
  • Finance (AREA)
  • Luminescent Compositions (AREA)
  • Credit Cards Or The Like (AREA)
  • Inspection Of Paper Currency And Valuable Securities (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Graft Or Block Polymers (AREA)
  • Burglar Alarm Systems (AREA)

Abstract

The invention concerns a printed valuable document with at least one authentication mark in the form of a luminescent substance based on a host lattice doped with at least one rare earth metal. The host lattice largely absorbs light in the entire visible region of the spectrum, is excitable in substantial parts of the visible region of the spectrum, and is at least partially transparent at least in the wavelength range between 0.8 mum and 1.1 mum. The host lattice also features a garnet or perovskite structure. The rare earth metal emits light in the wavelength range between 0.8 mum and 1.1 mum.

Description

The valuable printed text that luminous discriminating mark is arranged
Technical field
The present invention relates to have the valuable document that at least one differentiates the printing of mark (authenticity feature), described mark is the form of luminescent substance, and this luminescent substance is based on the host lattice that is doped with at least a rare earth metal.
Background technology
People have known with luminescent substance and have protected valuable document for a long time.The use of rare earth element is also existing in this respect discusses.These rare earth metals have the distinctive especially narrow spectral line of emission at infrared spectral region, therefore, when using measuring technique, can be different from the spectral line of emission of other material reliably.False proof in order further to strengthen, rare earth metal and other material can be mixed together forming host lattice, thereby influence exciting of rare earth metal and/or emission spectrum in the mode of feature.By combining with suitable absorbent material, for example, the part that can suppress rare earth metal excites and/or emission band.But for example by the specific region of decay broadband spectral, this influence also can be the form of " distortion ".
Similarly, false proof in order to strengthen, use the spectral line of emission to be higher than the rare earth metal of 1500 nanometers usually, far away more because the spectral line of emission is positioned at infrared spectral region, the detection of the spectral line of emission becomes and becomes increasingly complex and difficulty.In general, applied principle is along with the radiation that will detect is slack-off, and the detectability of photoelectric detector reduces, and this is because signal to noise ratio reduces under identical ratio; Promptly the signal of Jian Ceing more and more is difficult to detect in noise.Therefore luminescent substance also must be present in the valuable document, so that can produce detected enough signal strength signal intensities in noise reliably.But, under some concrete condition, can not produce and detect necessary these limting concentrations; For example, when luminescent substance has the color of himself, when luminescent substance mixed with valuable document, this color had been damaged required print color (Farbeindruck).In some cases, also attempt to reduce danger, because luminescent substance only uses with very little concentration by the luminescent substance that is contained in the chemical analysis valuable document.
In these cases, even must avoid using those under low concentration, also can detect the luminescent substance of the spectral line of emission.
Therefore, the present invention is based on the purpose of producing the valuable document with luminescent substance, the spectral line of emission of this luminescent substance is positioned at narrow infrared spectral region, thereby even also can detect the existence of luminescent substance under low concentration in valuable document.
Summary of the invention
The present invention is specifically related to have the valuable document that at least one differentiates the printing of mark, described mark is the form of luminescent substance, this luminescent substance is based on the host lattice that is doped with at least a rare earth metal, this host lattice absorbs in whole visible range basically, can excite in most of visible range, and in the wave-length coverage of 0.8-1.1 micron, be partially transparent at least, rare earth metal is launched in the wave-length coverage of 0.8-1.1 micron in this case, and host lattice has garnet or perovskite structure.
The valuable document of above-mentioned printing is characterized in that, rare earth metal is Yb, Pr or Nd.
The valuable document of above-mentioned printing is characterized in that, host lattice uses chromium as absorbing constituent.
The valuable document of above-mentioned printing is characterized in that, the garnet structure can be used general formula A 3Cr 5-xAl xO 12Describe, wherein A represents to be selected from the element of Sc, Y, La system or actinium series, index x 0＜x＜4.99 that satisfy condition.
The valuable document of above-mentioned printing is characterized in that, index x 0＜x＜2.5 that satisfy condition.
The valuable document of above-mentioned printing is characterized in that, luminescent substance can be used general formula Y 3-zD zCr 5-xAl xO 12Describe, wherein D represents Nd, Pr or Yb, index z 0＜z＜1 that satisfies condition.
The valuable document of above-mentioned printing is characterized in that, perovskite structure can be used general formula ACrO 3Describe, wherein A represents element Y, Sc or La series elements.
The valuable document of described printing is characterized in that, luminescent substance can be used general formula Y 1-zD zCrO 3Wherein D representative element Nd, Pr or Yb, index z 0＜z＜1 that satisfies condition is described.
The valuable document of above-mentioned printing is characterized in that, luminescent substance is sneaked in the printing-ink, and this printing ink contains the visible colour additive that has in addition.
The valuable document of above-mentioned printing is characterized in that luminescent substance is sneaked in the paper pulp.
The valuable document of above-mentioned printing is characterized in that, luminescent substance is arranged on the carrier mass or in it, this carrier mass to small part is imbedded in the paper pulp.
The valuable document of above-mentioned printing is characterized in that carrier mass is made of plastics.
The valuable document of above-mentioned printing is characterized in that, carrier mass is the form of safety line or composite fibre.
The valuable document of above-mentioned printing is characterized in that, luminescent substance with sightless, be that the sightless coating of part is arranged on the valuable document at least.
The valuable document of above-mentioned printing is characterized in that, coating is the form of bar.
The invention still further relates to false proof device with at least a carrier mass and a kind of luminescent substance, this luminescent substance is based on the host lattice that is doped with at least a rare earth metal, this host lattice absorbs in whole visible range basically, can excite in most of visible range, and in the wave-length coverage of 0.8-1.1 micron, be partially transparent at least, rare earth metal is launched in the wave-length coverage of 0.8-1.1 micron in this case, and host lattice has garnet or perovskite structure.
Above-mentioned false proof device is characterized in that, luminescent substance is arranged in the volume of carrier mass.
Above-mentioned false proof device is characterized in that, luminescent substance exists with the concentration of 0.01-10% weight, preferred 0.1-5% weight in the carrier band material.
Above-mentioned false proof device is characterized in that, luminescent substance exists with the form that is administered to the layer on the carrier mass.
Above-mentioned false proof device is characterized in that, luminescent substance is with the 0.5-40% weight concentration, preferably the concentration range with 20-30% weight is present in the printing-ink.
Above-mentioned false proof device is characterized in that carrier mass is made of plastics.
Above-mentioned false proof device is characterized in that carrier mass is made of paper.
Above-mentioned false proof device is characterized in that, carrier mass is the form of safety line, blended fiber, flower shape or label.
Valuable document according to the present invention contains at least a luminescent substance, and this luminescent substance is based on the host lattice that is doped with rare earth metal, and in this case, the emission of rare earth metal is positioned at narrow infrared spectral region, promptly in the wave-length coverage of 0.8-1.1 micron.The advantage of this launch site is with silicon (Si), GaAs (GaAs), Gallium indium arsenide (Ga xIn X-1As) or germanium (Ge) photoelectric detector can detect its existence easily because these detectors have quite high response sensitivity in this wave-length coverage.As the optical activity rare earth metal, admissible in this case element is ytterbium (Yb), neodymium (Nd) or praseodymium (Pr), or the mixture of these elements and one or more other rare earth metals.
These rare earth metals are embedded in the host lattice that the visible range has effective excitation band, and these excitation bands are transferred to rare earth metal.Effectively excitation band can according to the present invention, be doped into the chromium component in garnet or the perovskite structure by realizing as the chromium part.
In this case, host lattice has optical window and in fact absorbs in whole visible range at narrow infrared spectral region, and the result is that all spectral lines of the visible range of luminescent substance will be suppressed.The radiation area of the lasing region of luminescent substance and intense light source (as Halogen lamp LED, flash lamp and similar light source) coincides.The result of this situation, and because the interior effective energy to rare earth metal of host lattice transmits, might in valuable document, use very a spot of luminescent substance according to the present invention, and can not limit the mechanical possibility of detection.But, detect especially difficulty because low concentration will make by chemical analysis.
The absorption composition of host lattice can be replaced by non-absorbent aluminum portions.Can control the brightness of absorption value and luminescent substance by the ratio of aluminium.Therefore, having such luminescent substance also can be as the additive of brighter printing ink.
By means of drawings and Examples, further embodiment of various details and benefit.
Description of drawings
Fig. 1 is the exciting light spectrogram that contains the host lattice of chromium according to the present invention,
Fig. 2 is the spectrogram of some light sources,
Fig. 3 is the emission spectrum figure that is doped with the luminescent substance of Pr according to the present invention,
Fig. 4 is the emission spectrum figure that is doped with the luminescent substance of Nd according to the present invention,
Fig. 5 is the emission spectrum figure that is doped with the luminescent substance of Yb according to the present invention,
Fig. 6 is the cross-sectional view of false proof device of the present invention.
The specific embodiment
Fig. 1 illustrates the exciting light spectrogram that contains the dot matrix of chromium of the present invention.This dot matrix almost absorbs in whole visible range.Because the absorption in the very broadband of this host lattice, the spectral line that is positioned at this regional rare earth metal doping is suppressed.Simultaneously, the energy from the dot matrix to the rare earth doping metal has taken place shifted, the result has caused the emission of luminescent substance.
The benefit of the wide band absorption of this dot matrix can use intense light source (as flash lamp) to come the stimulated luminescence material in addition, and this light source produces radiation in whole visible range equally.
Fig. 2 illustrates the spectrogram of this flash lamp, and label is 1.The spectrum 1 of the flash lamp that illustrates extends to infrared region continuously from the ultraviolet spectra district.In some cases, also can only penetrate luminescent substance with the illumination of visible range.In this case, provide suitable wavelengths with light emitting diode (LED) irradiation.Light emitting diode has narrow-band spectrum usually, therefore, in order to cover whole spectral regions, needs several LED.Fig. 2 illustrates the spectrogram of green, orange and red LED.
Fig. 3,4 and 5 illustrate the spectral radiance map according to single luminescent substance of the present invention.
Fig. 3 illustrates the spectral radiance map of the host lattice of mixing with Pr.The scope of spectrogram is the 0.9-1.08 micron.It has the emission peak number that has feature, and this peak can make us very being rated as satisfactorily diagnostic characteristics.
Fig. 4 illustrates the feature spectrogram of the dot matrix that is doped with Nd.This spectrogram about 0.9 micron to just having two great emission peaks in the scope under 1.1 microns.In addition, in 0.95 micron scope, has an a little bit smaller slightly peak.
The spectrogram of the dot matrix that Yb shown in Figure 5 mixes is very symmetrical, and has only a peak that its maximum is at 1.0 microns in contrast.
Something in common according to all these dot matrix of the present invention is that they have luminescence emissions clearly at narrow infrared region (promptly in the scope of 0.8-1.1 micron), and this is to be difficult to confirm.Although these three emission spectrum are all in the identical spectra scope, their differences each other are so obviously so that to distinguish with the commercial measurement method be feasible.
In order to ensure the efficient of the maximum possible of rare earth metal, under the situation of garnet structure, use general formula to be A 3Cr 5-xAl xO 12Host lattice, wherein A represents to be selected from the element of Sc, Y, La system or actinium series, index x 0＜x＜4.99 that satisfy condition, preferred 0.3＜x＜2.5.
An embodiment preferred according to luminescent substance of the present invention is Y 3-zD zCr 5-xAl xO 12, wherein D represents Nd, Pr or Yb, index z 0＜z＜1 that satisfies condition.
If host lattice is perovskite structure, can use general formula ACrO 3Describe, wherein A represents the element of element Y, Sc or La system.
One preferred embodiment of luminescent substance of the present invention is to use general formula Y 1-zD zCrO 3The perovskite structure of describing, among D representative element Nd, Pr or the Yb wherein, index z 0＜z＜1 that satisfies condition.
Describe luminescent substance of the present invention in detail by means of several embodiment below.
Embodiment
Embodiment 1
Garnet (the Y that the Y-Al-Cr of Nd activation mixes 2.95Nd 0.05Cr 4Al 1O 12) production:
With 47.82 gram Y 2O 3, 7.32 the gram Al 2O 3, 43.65 the gram Cr 2O 3, 1.21 the gram Nd 2O 3With the dry sodium sulphate (Na of 100 grams 2SO 4) mix fully, and in the diamond dust crucible, be heated to 1100 ℃ 12 hours.
After cooling, the griding reaction product, water washes out fusion agent, and the sodium chromate that forms as accessory substance is reduced to chromium sulfate (III) with sulfuric acid/ferrous sulfate, then 100 ℃ of air dryings.In order to reach possible fine grain, in water, grind powder till average grain diameter is less than 1 micron with a mill ball grinding machine.
After filtration and the drying, obtain green powder.
Embodiment 2
Garnet (the Y that the Y-Al-Cr of Yb activation mixes 2.7Yb 0.3Cr 3Al 2O 12) production:
With 43.93 gram Y 2O 3, 14.69 the gram Al 2O 3, 32.86 the gram Cr 2O 3, 8.52 the gram Yb 2O 3With the dry sodium sulphate (Na of 100 grams 2SO 4) mix fully, and in the diamond dust crucible, be heated to 1100 ℃ 12 hours.
After cooling, the griding reaction product, water washes out fusion agent, and the sodium chromate that forms as accessory substance is reduced to chromium sulfate (III) with sulfuric acid/ferrous sulfate, then 100 ℃ of air dryings.In order to reach possible fine grain, in water, suitably grind powder with a mill ball grinding machine.
After filtration and the drying, obtain green powder, its average grain diameter is less than 1 micron.
Embodiment 3
Garnet (the Y that the Y-Al-Cr of Pr activation mixes 2.98Pr 0.02Cr 2.4Al 2.6O 12) production:
With 51.39 gram Y 2O 3, 20.24 the gram Al 2O 3, 27.86 the gram Cr 2O 3, 0.5 the gram Pr 2O 3With the dry sodium sulphate (Na of 100 grams 2SO 4) mix fully, and in the diamond dust crucible, be heated to 1100 ℃ 12 hours.
After cooling, the griding reaction product, water washes out fusion agent, and the sodium chromate that forms as accessory substance becomes chromium sulfate (III) with sulfuric acid/ferrous sulfate reduction, then 100 ℃ of air dryings.In order to reach possible fine grain, in water, suitably grind powder with a mill ball grinding machine.
After filtration and the drying, obtain the light green powder, its average grain diameter is less than 1 micron.
Embodiment 4
Y-Cr perovskite (the Y of Nd activation 0.95Nd 0.05CrO 3) production:
With 55.96 gram Y 2O 3, 39.65 the gram Cr 2O 3, 4.39 the gram Nd 2O 3With the dry sodium sulphate (Na of 100 grams 2SO 4) mix fully, and in the diamond dust crucible, be heated to 1100 ℃ 20 hours.
After cooling, the griding reaction product, water washes out fusion agent, and the sodium chromate that forms as accessory substance is reduced to chromium sulfate (III) with sulfuric acid/ferrous sulfate, then 100 ℃ of air dryings.In order to reach possible fine grain, in water, suitably grind powder with a mill ball grinding machine.
After filtration and the drying, obtain the light green powder, its average grain diameter is less than 1 micron.
According to the present invention, can luminescent substance be joined in the value documents with multiple mode.For example, luminescent substance can be added in the printing-ink, this printing-ink also contains macroscopic colorant.Also luminescent substance can be sneaked in the paper pulp.Similarly, also luminescent substance can be applied on the plastic carrier material or wherein, for example this carrier mass to small part is imbedded in the paper pulp.Carrier mass can be the form of safety line, blended fiber or flower shape in this case.
But plastics or paper carrier mass also can be fixed on any other required object, as are used for the safeguard measure of product.In this case, carrier mass is preferably with the form production of label.If carrier mass is a part of the product that will protect,, also may be any other shape certainly as under the situation of the band that can tear by dotted line.In some purposes, it may be useful providing luminescent substance with the form of the invisible coating on the value documents.In this case, luminescent substance may reside on the whole surface or exists with the form of specific shape such as strip, wire, ring-type or alphanumeric indicia.
In the present invention, term " valuable document " refers to banknote, check, stock, stamp, identity card, credit card, passport and other file, and label, sealing, packs or be used for other object of product protection.
Fig. 6 shows the embodiment of false proof device of the present invention.In this case, false proof device is made of label 5, and it comprises paper or plastic layer 6, transparent covering layer 7 and adhesive phase 8.Label 5 is connected on the required substrate 10 by adhesive phase 8.This substrate 10 can be valuable document, identity card, passport, certificate or similar article or other file that will protect, as CD, packing or analog.
In this embodiment, luminescent substance 9 is included in the layer scope of layer 6.If layer 6 is one deck paper, then the concentration of luminescent substance is 0.05-1% weight.
On the other hand, luminescent substance also can be included in the unshowned here printing-ink, and it is printed on one of label layer, preferably on the surface of layer 6.In this case, the concentration of the luminescent substance in the printing-ink changes between 10-30% weight.
Except being arranged on luminescent substance on the carrier mass or in it; and then outside being fixed on the object as false proof device this carrier mass, also luminescent substance can be set directly at according to the present invention in the valuable document that will protect or in its surface with the form setting of coating.

Claims (27)

1. has the valuable document that at least one differentiates the printing of mark, described mark is the form of luminescent substance, this luminescent substance is based on the host lattice that is doped with at least a rare earth metal, this host lattice absorbs in whole visible range basically, can excite in most of visible range, and in the wave-length coverage of 0.8-1.1 micron, be partially transparent at least, rare earth metal is launched in the wave-length coverage of 0.8-1.1 micron in this case, and host lattice has garnet or perovskite structure.
2. according to the valuable document of the printing of claim 1, it is characterized in that rare earth metal is Yb, Pr or Nd.
3. according to the valuable document of the printing of claim 1, it is characterized in that, host lattice with chromium as absorbing constituent.
4. according to the valuable document of the printing of claim 1, it is characterized in that the garnet structure can be used general formula A 3Cr 5-xAl xO 12Describe, wherein A represents to be selected from the element of Sc, Y, La system or actinium series, index x 0＜x＜4.99 that satisfy condition.
5. according to the valuable document of the printing of claim 4, it is characterized in that index x 0＜x＜2.5 that satisfy condition.
6. according to the valuable document of the printing of claim 4, it is characterized in that luminescent substance can be used general formula Y 3-zD zCr 5-xAl xO 12Describe, wherein D represents Nd, Pr or Yb, index z 0＜z＜1 that satisfies condition.
7. according to the valuable document of the printing of claim 1, it is characterized in that perovskite structure can be used general formula ACrO 3Describe, wherein A represents element Y, Sc or La series elements.
8. according to the valuable document of the printing of claim 7, it is characterized in that luminescent substance can be used general formula Y 1-zD zCrO 3Wherein D representative element Nd, Pr or Yb, index z 0＜z＜1 that satisfies condition is described.
9. according at least one the valuable document of printing among the claim 1-8, it is characterized in that luminescent substance is sneaked in the printing-ink, this printing ink contains the visible colour additive that has in addition.
10. according at least one the valuable document of printing among the claim 1-8, it is characterized in that luminescent substance is sneaked in the paper pulp.
11., it is characterized in that luminescent substance is arranged on the carrier mass or in it, this carrier mass to small part is imbedded in the paper pulp according at least one the valuable document of printing among the claim 1-8.
12. the valuable document according to the printing of claim 11 is characterized in that carrier mass is made of plastics.
13. the valuable document according to the printing of claim 11 is characterized in that carrier mass is the form of safety line or composite fibre.
14. according at least one the valuable document of printing among the claim 1-8, it is characterized in that, luminescent substance with sightless, be that the sightless coating of part is arranged on the valuable document at least.
15. the valuable document according to the printing of claim 14 is characterized in that coating is the form of bar.
16. have the false proof device of at least a carrier mass and a kind of luminescent substance, this luminescent substance is based on the host lattice that is doped with at least a rare earth metal, this host lattice absorbs in whole visible range basically, can excite in most of visible range, and in the wave-length coverage of 0.8-1.1 micron, be partially transparent at least, rare earth metal is launched in the wave-length coverage of 0.8-1.1 micron in this case, and host lattice has garnet or perovskite structure.
17. the false proof device according to claim 16 is characterized in that, luminescent substance is arranged in the volume of carrier mass.
18. the false proof device according to claim 17 is characterized in that, luminescent substance exists with the concentration of 0.01-10% weight in the carrier band material.
19. the false proof device according to claim 17 is characterized in that, luminescent substance exists with the concentration of 0.1-5% weight in the carrier band material.
20. the false proof device according to claim 16 is characterized in that, luminescent substance exists with the form that is administered to the layer on the carrier mass.
21. the false proof device according to claim 20 is characterized in that, luminescent substance is present in the printing-ink with 0.5-40% weight concentration scope.
22. the false proof device according to claim 20 is characterized in that, luminescent substance is present in the printing-ink with the concentration range of 20-30% weight.
23., it is characterized in that carrier mass is made of plastics according at least one false proof device among the claim 16-22.
24., it is characterized in that carrier mass is made of paper according at least one false proof device among the claim 16-22.
25., it is characterized in that carrier mass is the form of safety line, blended fiber, flower shape or label according at least one false proof device among the claim 16-22.
26. the false proof device according to claim 23 is characterized in that, carrier mass is the form of safety line, blended fiber, flower shape or label.
27. the false proof device according to claim 24 is characterized in that, carrier mass is the form of safety line, blended fiber, flower shape or label.
CNB998001015A 1998-02-02 1999-01-29 Valuable printed document with luminous discriminator Expired - Lifetime CN1142866C (en)

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DE19803997.2A DE19803997B4 (en) 1998-02-02 1998-02-02 value document
DE19803997.2 1998-02-02

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CN1142866C true CN1142866C (en) 2004-03-24

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EP (1) EP0977670B1 (en)
CN (1) CN1142866C (en)
AT (1) ATE281940T1 (en)
AU (1) AU2721199A (en)
BR (1) BR9904819B1 (en)
DE (2) DE19803997B4 (en)
HK (1) HK1027323A1 (en)
NO (1) NO994741D0 (en)
RU (1) RU2191119C2 (en)
WO (1) WO1999038703A1 (en)

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US6383618B1 (en) 2002-05-07
ATE281940T1 (en) 2004-11-15
WO1999038703A1 (en) 1999-08-05
CN1255897A (en) 2000-06-07
BR9904819A (en) 2000-05-23
DE19803997A1 (en) 1999-08-05
NO994741L (en) 1999-09-29
DE19803997B4 (en) 2018-01-25
RU2191119C2 (en) 2002-10-20
DE59911029D1 (en) 2004-12-16
EP0977670B1 (en) 2004-11-10
BR9904819B1 (en) 2008-11-18
NO994741D0 (en) 1999-09-29
HK1027323A1 (en) 2001-01-12
AU2721199A (en) 1999-08-16
EP0977670A1 (en) 2000-02-09

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